Chlorinated terpene alcohols, esters, and ethers as insecticides



Patented Oct. 27, 1953 CHLORINATED' TERPENE-.. ALCOHOLS,

ESTER/S; AND. 'ETHEBS lASLINSECTI CIDES QE-FILC Willi'am-D;"Stonecipher,Newark, Del., assignor toaHercules Powder Company, Wilmington, DeL, acorporation of Delaware No Drawing; Application October '7, 1950, SerialNo. 189,071

5 Claims: 1

This invention relates .to .an insecticidal. com,-

position andmore particularlyto an insecticidal.

composition containing. a chlorinated cyclic .oxye terpene derivative asthe toxic ingredients.

Among the more commonly used insecticidalv toxicants. are the naturallyoccuring. products, pyrethrum,. rotenone, and .nicotine. These nat-.

uraLprodricts have the very great disadvantage in.-.not beinguniform.inv their insecticidal activity. Many syntheticproducts have beensuggested in the past as substitutes for these toxicants; however, theyare "usually lacking in one respector. another; Particularly they do.not

usually have a high enough killingpower and.

must beused in concentrations whichlcause irritation to the user, or ifthey, are sufliciently;

toxic,.they are also toxic toformsofanimallife other .than .insectpests.

N owinv .accordance with this invention,. it has been found thatinsecticidal compositions con-.

taining as a toxic ingredient a chlorinated cyclic.oxyterpenederivative, having a .chlorine content ofa-fromaabout 40% toabout. 70%, possessan.

unusual degree of insecticidal activity. These chlorinated cyclicoxyterpene derivatives which may be prepared bychlorinating such cyclicoxyterpenes as cyclic terpeneacylates, cyclic terpener. alcohols. cyclicterpeneethers, cyclic. terpene- Approximately 100 five-day o1d-fiies--(Mason-.1 domestica) were placed in a bell jar and a predeterminedquantity ,of the insecticide to be tested was atomized 'iin'tdthebellljar. 'I'h'eouantityv of insecticide used wasequal .to.th'eamount'of the ofiicial test insecticide which was necessary to give a30-55% killxandz'must be within the limits of 0.4 to 0.6 ml. Afterspraying the insecticide :into* the chamberpthe fiieswerepiaiced. in'ranobservation'cage containing a wadof'fcot-i ton wetiwitha dilute sugarsolution; At the end" of24 hours; the number ofde'ad'and moribundflies'was counted. All "testswere" carried- =out-"at 80-90'F. and 50'70'% relativehumi'dity."

Insecticidal tests Werewimade :on..-'.1% solutions of the twochlorinated isobornyl acetates..in..de.-.. odorized kerosene Bell jar'tests' on flies- Percent O T I v Percent Chlorine lgfafiil lllnDmerenceh equaLto an O. T.. I. difference of +64.

'I'v'vo parts of isobornyl acetate dissolved in 1" part of carbontetrachloride was "placed in'a chlorination vessel and a crystal of-iodine was chloride'was distilled ofi under. reduced pressure: This.material. was a yellow liquid which had a chlorine contentiof 40.1%.

It was fractionated. g

under reduced'pressureand the twoifractionsi having ,a chlorine contentofv 44.7% and ;'47.'8.%.

were tested for their insecticidal activity against In this and thefollowing..examples,

themtest for insecticidal l activit'y against house:

flies was made in .the following .manner and. 'is referred toin thisspecification as. the .bell'jar 4 a method.

The same chlorinated isobornyl acetate (418%. Cl) was als'otested incombination with the official. test insecticide. When 0.2% of thismaterial was added 'to the official test insecticide. atkill; of. 921%was obtained whichcorresponded toan". increase overitheOIT. I. alone of+61.

EXAMPLE :II T

The chlorinated isobornyl acetate containing" 47.8% chlorine, which wasdescribed in Example I, was testedforits' insecticidal activity againsvadultmale German roaches? In carrying out: this test; 10*'to"15 "roacheswere placed in "cages" and sprayed with *deodorizedz-kerosene solutionsof the toxicant. A 2.5% and a 5% solution in deodorized kerosene.of'this material gave a"k'ill which Was,equ al to. theJOJ TiL A10%;de.-" odorized. kerosene .solution of the material gave"- a'1003%killiwhiclr'was.'equal to'an-OJ T. Ifidif 3 EXAMPLE 111 BelZ jartests on flies Concentrations of Deodorized Kerosene gigfi O.T.I.

utions Difierence 24 Hrs.

When tested on German roaches as described in Example II, a 10% solutionin deodorized kerosene gave a kill of 100%.

EXAMPLE IV Chlorinated isobornyl acetates (prepared by chlorinatingisobornyl chloroacetate by the chlorination procedure described inExample I) containing 43.3% chlorine and 47.3% chlorine were tested fortheir insecticidal activity against houseflies by the bell jar method.

Bell jar tests on flies Concentra- Percent Percent Chlorine f gg f gggjDead in O.T.I.

24 Hrs. cent EXAMPLE V A chlorinated isobornyl acetate prepared bychlorinating isobornyl chloroacetate and a chlorine content of 42.7%. A1% solution in deodorized kerosene when tested against house- :dies bythe bell jar method gave an increase in kill over the O. T. I. of 35.When 0.5% of this material was added to the O. T. I., an increase inkill of 34 over the O. T. I. alone was obtained.

This product was also tested against the German roaches as described inExample II. A solution in deodorized kerosene of this chicrinatedisobornyl acetate gave a kill of 100%.

EXAMPLE VI One part of bornyl salicylate was dissolved in 3 parts ofchloroform. A small crystal of iodine was added as catalyst and chlorinewas bubbled through the solution until the exothermic reaction ceased.The reaction mixture was then diluted with petroleum ether, washed withsodium bicarbonate solution until free of acid and excess chlorine anddried over sodium sulfate. The solvent was removed by distillation underreduced pressure and the product which r mained was an orange-coloredvery viscous liquid which had a chlorine content of 41.8%. A 10%deodorized kerosene solution of this chlorinated bornyl salicylate whentested for its insecticidal activity against houseflies by the bell jarmethod had a kill of which was equal to an O. T. I. difference of +54.

EXAMPLE VII One and one-half parts of isoborneol was dissolved in 2parts of carbon tetrachloride and a small crystal of iodine was added asa catalyst. Chlorine was passed into the solution for 4 hours, thetemperature rising to 62 C. and then decreasing as the chlorinationproceeded. Diethyl ether was then added to the reaction mixture and themass was water washed and dried. The solvent was removed by distillationunder reduced pressure and a viscous yellow liquid, which had a chlorinecontent of 40.8%, was obtained.

The chlorinated isoborneol was tested for its insecticidal activityagainst houseflies by the bell jar method. A 1% solution of thismaterial 'in deodorized kerosene had a kill of 44% which was equal to anO. T. I. difference of +6.

EXAMPLE VIII One part of fenchyl alcohol dissolved in 5 parts of carbontetrachloride was placed in a chlorination vessel and exposed toultraviolet illumination. Chlorine was passed into the agitated mixtureat a rate that allowed for maximum absorption of the chlorine. Thechlorination was continued until 4 parts of chlorine had been absorbed.The carbon tetrachloride was removed by distillation under reducedpressure. The chlorinated fenchyl alcohol so obtained was a very viscousyellow liquid having a chlorine content of 61.3%.

This chlorinated fenchyl alcohol was tested for its insecticidalactivity against housefiies by the bell jar method. The results obtainedon deodorized kerosene solutions of this material are given in thefollowing table:

Bell jar tests on flies 10% solution of this toxicant.

EXAMPLE IX One part of fi-chloroethyl terpinyi ether dissolved in 5parts of carbon tetrachloride was chlorinated by passing chlorine intothe solution in the presence of ultraviolet light, the temperature beingheld below 45 C. during the chlorination. After 8 hours of chlorinationa portion of the material was removed and the remainder was chlorinatedfor a total of 24 hours. The carbon tetrachloride was removed from eachof the two materials by distillation under reduced pressure. The twochlorinated ,B-chloroethyl terpinyl ethers so obtained were yellowliquids having a chlorine content of 60.8% and 66.4%, respectively.

The chlorinated T cyclic .oxyterpene derivative. containing'from about40%500 -ab'out"70%- ch10 rine which is used .as the toxic,ingredientvoffth'el insecticidar' compositions ofs' th'i's' invention.is a chlorinated cyclic terpene alcohol} a-chlorinated'. ester, of acyclicterpenealcohol, and an organic; carboxylic. acid; having; not?more. thanmseven carbon atoms-inth'e molecule, .or a chlorinated etherof: at least one cycliclte'rpene aleoholwhaving no more than 20.carbonatomsper molecule.

The cyclichterpene alcoholslwhich arel.vchlo-. rin'ated to, 40% to 70%Lchlorine. foruse in H the. insecticidal.compositions 10f 'thiswinventionare; borneol,. isoborneol, fenchylw alcoholsg isofe'nchyl. alcohols,terpineols,. terpinenols menthol; carvomenthol, carveol, .terp'in-1,4,terpin-1-,.8,.and the like. The bicyclic terpene. alcohols Whichtarechlorinated to .tov 70 chlorine content-are the: most toxic of thechlorinatedterpene alcohols. The positiomof: the alcohol group isnof.less.- importance thanthe percentage: chlorinei-infl 35 the molecule,butjregardless of the position:of-= the -alcohol group in the-molecule,-thetchlorinated-- cyclic terpene alcohols-all possess; insecticidalsproperties when made==into the rcompositions of: this invention, Theoxygen analysis of the: =chlo-.- rinated cyclic' terpenealcoholssindicates -that the oxygen isnot 10st in .thechlorinationprocess;

The-chlorinated;- esters-of cyclic terpene also hols .and- -organ-iccarboxylic acids having; not,

more than .7 oarbonatomsiare' Obtain6dobyqCh10-w45 v,

rination 1 ofthe esters of the previously listed 1 cyclioterpenealcoholsa The organic acids which are: combined with these---alcohols toiormtthese esters priorto tchlorinationa: are: thesaliphaticeacids,formiaacetic', propionic; loutyr-imisolmztyricy- 501.

Valerie hexanoic and heptanoic acidsg the =aro= matio acids, benzoic;acid-5: salicylic-acidit-anchtoluic' acids the. dibasic-acids; oxalicacid, maleic a". acid, ,succinic scacid; glutaricacid, ,(adipic ,acid'pimelic acid-, phthalic. acid:andterephthalimacid and thealicyclicacids; hexahydrobenzoioaiacid tetrahydroloenzoic-;acid-,-.hexahydrotoluie acid s'a-nctrt tetrahydrotoluic: aeid;-andachlorineasubstitutedi acidswhich. are derivedfromitheaboveiacidstbym chlorination. The 1 chlorineiainithevchlorinat-ion: 1.

process enters to a large extent thecterp eneral-.- cohol-part of theestereand v -those Jesters .inswhi'ch at least one-half of :thechlorinefcontentwriseinn thetterpene alcohol part ofstheschlorinated tehpene ester are themost =efiective =of.-2the2:chlo nated cyclic terpene.esters :aswinsecticidesa Ese ters of cyclic terpene;-alcoholssand= fchlorinated; organic V acidsiare; chlorinatedoto produce. chloratrinated. esters of cyclic-terpene alcohols! and or:

least 20% chlorine in}, the :terpene partotethet 'tqa molecule ion achlorinated. cyclic,terpenerasterw having atileast" 40%"jtotalichIorineiirfzthimolee; 011113;; The chlorinated, cyclic; terpene 'estersilbwanalysis stillcontain oxygen;

The chlorinated ethers of 'cycliclxterpene. .al cohols. are ,etherstheoretically,derived 1mm, one. cyclic terpene alcoholganduanonterpenoid "on-.J garlic; alcohol or ethers ,theoretically;derived;from two-cyclic terpene alcohols-or, ,in' the case. of..'tlie cin'eoles,internal iethers. of onemcyclicwterr, pene alcohol; It" is.not.-;in;tendedlto.\limit'.thela ether to anyparticularimethodt'bfits-.preparaa tion. In lithe case of, the mix'edeethersfi theaor; ganiclalcohol portion is. alcohol; havingyl-notr c more than? 101 carbonatoms... The .snonte'rpenoidi alcohol portion of the ether. may. contain-chloa. rin'e but) atoleast oneehalf ofivtheiotalnchl'ormei iniitheproduct mustibelin the cycliceterpenelalT- coh'ol part or the molecule;The cyclic terpene alcohols which 7 form. the etherst-which are ch10:

rinated for use in ithis'i. invention -aremthosalisted; above; Thenonte'rpenoidMalcoholshwhicha.form.- the ethers with. thelterpenealcohols which "are chlorinated are methyl alcohol, ethyl alcohol;propylgalcohol, isopropyl alcohol,,butyllalcoholsisamyl' alcohols,hexyl. alcohols; .heptyl alcohols," octyl alcohols, nonyl 'Ialcohols,.ldecyli alcohols cyclo'hexanol, cyclopentanol fmethyl .cyclohexana 01,and chlorine -substituter;lalcoholswhereinthe chlorine is less than that.which Lwouldn produce". an ether of the cyclic terpene alcohol havingmore than about 20% chlorine in thevether which is to be chlorinated.Chlorinated 'eth'ersioficyclic-a terpene. alcohols and" nonterpenoidaalcohols which have the highest toxicity haveiativleastu one-half of thenecessarychlorine in,thel.cyclic.q terpene alcohol part ofjthe ether.The chlorine, ated cyclic terpene ethershaving -401%--to.Yv-l%ll totalchlorine inthe molecule still containicom= bined oxygen and are.allefie'ctive in theinsectie cidal "compositions of this invention.

Any of the chlorinated oyclicoxyterpene deriva atives' containing Ir'omabout" 40%,j.'to' iabout'i'l (1% chlorine maybe usedgasihex-toxicingredient of; the insecticidal compositions ofgthis .invention..

The chlorinated cyclidoxyte'rpene, derivativesv of this invention are.of yunknownh-structurei inthat .the position of the chlorine atoms 1is. .un.-. known: However, thexringsystem .ofj'the cyclic; terpenes isbelieved. to remain unchanged. They} are'made" by... chlorination oflithe .cyclic' oxyte'rn pene derivative under a wideirange1ofjchlorina=tion' conditions. and the product is believed to.. be "a. mixture of.chlorinated? cyclic oxyte'rpenei derivative isomers.similarw'mixtures.have'Jbeen... prepared "under a wide range of vchlclrination con: ditiohs'and the toxicity to flies has beenllfo'undflto be. relatively independent-ofthe.methodl,of chlorination, b'utto.-bedepe dent 'ratherluponn the degree 'of chlorination? The chlorinatedfcyclic' loxyterpene, derivativesare" prepared by chlorination! oflnthecyclic oxy-l terpene. derivative at .a temperatureorbeldwcthedecomposition point oiithelprodlictw Mostmchloe rinatedfvcyclicnoxyterpene v derivatives mtendatot decompose-- at itheirlboiling: points .andLtha chlorinationis, .therefore carriedsout belowthe. boil-.- ing temperaturel ofjtha material: jbeing chlorins ated.l.The temperature loin chlorinationmis gen-=- gan ic acids],ofthisinventioma The toxicity ofiy erally,keptebeloiw.aboutpldofiC;-andichlorination temperatures-W thee rateaofnchlorination im-l-l initialvtstagesiof,chlorination-:mayme, C3,r,ried,-Qut scene 7 at low temperatures, the final stagesof chlorine ationshould be carried out above 50 C. in order to reach a sufiiciently highchlorine content to reach the desired toxicity.

The chlorination may be carried out in the presence or absence ofcatalysts but the reaction rate may become impractically slow,especially toward the end of the chlorination, in the absence ofcatalysts and catalysts are, therefore, generally used for practicaloperation. Light is one of the most satisfactory catalysts and this ispreferably actinic light. It acts by accelerating the formation of freeradicals. Other catalysts may also be used by adding them to thechlorination mixture either at the beginning, during the course of, ortoward the end of the chlorination process. As catalysts, one may useiodine or one may use free radical formers such as lead alkyls ororganic peroxides including peroxy acids and peroxy anhydrides includingbenzoyl peroxide and acetyl peroxide. Only a catalytic amount ofcatalyst is needed and, if used up in the process, more will be added asrequired. More than a catalytic amount will not ordinarily be added atone time since better control is obtained by using only as much as isnecessary for attaining the desired rate of chlorination. The amount ofcatalyst used in the chlorination will ordinarily be within the range ofabout 0.001 to based upon the chlorination mixture.

The chlorination is generally carried out in the liquid state. Forinstance, a volatile chlorinated solvent such as methylene chloride,chloroform, carbon tetrachloride, ethylene chloride, trichloroethane,tetrachloroethane, or pentachloroethane is generally used in order tomain tain the liquid state and to reduce the viscosity sufiiciently forgood contact. Any well-known means of contacting the chlorine with thecyclic oxyterpene derivatives may be used. A satis factory methodinvolves dispersing chlorine gas in the liquid and relying on the flowof the gas for agitation. Auxiliary agitation may also be supplied.Since the reaction is ordinarily carried out at atmospheric pressure,the solvent is chosen according to its boiling point so that therefluxing solvent can provide a satisfactory means of temperaturecontrol. When a solvent is used, the amount ordinarily is kept belowabout volumes per volume of cyclic oxyterpene derivatives beingchlorinated and is generally within the range of 1-5 volumes per volumeof cyclic oxyterpene derivative. The chlorine is supplied to thereaction mixture at a rate substantially equal to that at which it isconsumed in the reaction.

The chlorinated cyclic oxyterpene derivatives may be readily purifiedand freed of catalysts by washing with water until sufiiciently free ofhydrochloric acid and then washing with mild alkali until neutral. Thecatalysts are ordinarily completely removed by this procedure. Afterpurification, the solvent is removed by distillation, preferably underreduced pressure.

The insecticidal compositions of this invention are produced by admixingthe chlorinated cyclic oxyterpene derivative having a chlorine contentwithin the range of about 40% to about 20% with a suitable adjuvantwhich is an inert material to facilitate the mechanical distribution ofthe chlorinated cyclic oxyterpene derivative toxin cant. Inert materialsto facilitate the mechanical distribution of the toxicant are added forthe purposes outlined in Frear (Chemistry of Incyclic oxyterpene bothaqueous sprays and dusts.

r 8 secticides, Fungicides, and Herbicides by Donald E. H. Frear, secondedition, 1948, page 5) to form sprays, dusts, and aerosols from thechlorinated derivative. Surface-active dispersing agents are used inadmixture with the chlorinated cyclic oxyterpene derivative to promotethe spreading of the toxic material so as to improve its effectiveness.They are used in Hydrocarbon solvents such as deodorized kerosene arealso used in sprays as the sole inert material to facilitate themechanical distribution of the toxicant. Suitable surface-activedispersing agents for use in the compositions of this invention arethose disclosed in Chemistry of Insecticides, Fungicides, and Herbicides(l. 0., pages 280-287) for use with known insecticides and include soapsof resin, alginic and fatty acids and alkali metals or alkali amines orammonia, saponins, gelatins, milk, soluble casein, flour and solubleproteins thereof, suliite lye, lignin pitch, sulfite liquor, long-chainfatty alcohols having 12-18 carbon atoms and alkali metal salts of thesulfates thereof, salts of sulfated fatty acids, salts of sulfonicacids, esters of long-chain fatty acids and polyhydric alcohols in whichalcohol groups are free, clays such as fullers earth, china clay,kaolin, and bentonite and related hydrated aluminum silicates having theproperty of forming a colloidal gel. Among the other surface-activedispersing agents which are useful in the compositions of this inventionare the omega-substituted polyethylene glycols of relatively longchainlength, particularly those in which the omega substituent is aryl,alkyl, or acyl. Compositions of the chlorinated cyclic oxyterpenederivative toxic material and surface-active dispelsing agent will insome instances have more than one surface-active dispersing agent for aparticular type of utility, or in addition to a surface-activedispersing agent, hydrocarbons such as kerosene and mineral oil willalso be added as improvers. Thus the toxic material may contain a clayas the sole adjuvant or clay and hydrocarbon, or clay and anothersurfaceactive dispersing agent to augment the dispersing action of theclay. Likewise, the toxic material may have water admixed therewithalong with the surface-active dispersing agent, sufficient generallybeing used to form an emulsion. All of these compositions of toxicmaterial and surface-active dispersing agent may contain in additionsynergists and/0r adhesive or sticking agents. Thus the chlorinatedcyclic oxyterpene derivative mixtures admixed with these inert materialswhich facilitate the mechanical distribution of the chlorinated cyclicoxyterpene derivative in accordance with this invention are thosecontaining the above-listed surface-active dispersing agents andhydrocarbon solvent dispersing agents.

The amount of chlorinated cyclic oxyterpene derivative in thecomposition with the inert mateIia-l which facilitates the mechanicaldistribution of the toxicant will depend upon the type of inert materialand the use to which it is to be put. The compositions will generallycontain less than about 30% chlorinated cyclic oxyter pene derivative.Agricultural dusts will generally contain l030% chlorinated cyclicoxyterpene derivative. Household sprays will contain from 0.1 to 10%chlorinated cyclic oxyterpene derivative. Agricultural sprays will,likewise, contain 0.1 to 10% of the chlorinated cyclic oxyterpenederivative. Aqueous emulsions will contain suflicient surface-activedispersing agent to maintain an emulsion of the chlorinated cyclicoxyterpene derivative during the spraying process.

For many purposes it may be desirable to use the chlorinated cyclicoxyterpene derivative in combination with other insecticidal toxicants.Many toxicants have a very high knockdown in relatively dilutesolutions, but higher concentrations must be used in order to obtain thedesired degree or kill. Due to the very high degree of killing owerwhich the chlorinated cyclic oxyterpene derivatives possess, thesecompounds may be added to such toxicants, thereby enabling the use ofmuch more dilute solutions than would otherwise be possible. Toxicantswith which these chlorinated cyclic oxyterpene derivatives may becombined include such compounds as rotenone, pyrethrum, and organicthiocyanates such as alkyl thiocyanates, thiocyanoethers such asfi-butoxy-p'-thiocyanoethyl ether, and terpene thiocyanoacylates such asisobornyl thiocyanoacetate, fenchyl thiocyanoacetate, isobornyla-thiocyanopropionate, etc.

The insecticidal compositions of this invention are useful in combattingflies, mosquitoes, roaches moths, carpet beetles, bedbugs, boll weevils,boll worms, army Worms, and grasshoppers and many other pests.

This application is a continuation-in-part of application Serial Number676,592, filed June 13, 1946, now abandoned.

What I claim and desire to protect by Letters Patent is:

1. An insecticidal composition comprising the product of chlorination inan inert solvent with chlorine gas in the resence of a freeradicalforming chlorination catalyst at a temperature in the range ofabout 50 C. to about 150 C. to a chlorine content of about 40-70% of anoxyterpene material of the group consisting of isobornyl acetate,isobornyl chloroacetate, isobornyl propionate, bornyl salicylate,fenchyl alcohol, isoborneol and terpinyl chloroethyl ether and aninsecticidal adjuvant as a carrier therefor.

2. An insecticidal composition comprising the product of chlorination ofisobornyl acetate in an inert solvent with chlorine gas in the presenceof a free radical-forming chlorination catalyst 10 at a temperature inthe range of about C. to about C. to a chlorine content of about 4070%and an insecticidal adjuvant as a carrier therefor.

3. An insecticidal composition comprising the product of chlorination ofisobornyl chloroacetate in an inert solvent with chlorine gas in thepresence of a free radical-forming chlorination catalyst at atemperature in the range of about 50 C. to about 150 C. to a chlorinecontent of about 40-70% and an insecticidal adjuvant as a carriertherefor.

4. An insecticidal composition comprising the product of chlorination ofisoborneol in an inert solvent with chlorine gas in the presence of afree radical-forming chlorination catalyst at a temperature in the rangeof about 50 C. to about 150 C. to a chlorine content of about 40-70% andan insecticidal adjuvant as a carrier therefor.

5. An insecticidal composition comprising the product of chlorination ofterpinyl ,B-chloroethyl ether in an inert solvent with chlorine gas inthe presence of a free radical-forming chlorination catalyst at atemperature in the range of about 50 C. to about 150 C. to a chlorinecontent of about 40-70% and an insecticidal adjuvant as a carriertherefor.

WILLIAM D. STONECIPHER.

References Cited in the file of this patent UNITED STATES PATENTS NumberName Date 1,755,1 8 Grant Apr. 22, 1930 2,160,579 Thompson, Jr May 30,1939 2,227,058 Borglin Dec. 31, 1940 2,347,929 Borglin May 2, 19442,565,471 Buntin Aug. 28, 1951 2,579,300 Buntin Dec. 18, 1951 OTHERREFERENCES Parker et al., University of Delaware Agr. Expt. StationBulletin Number 264, Tech. No. 36, entitled, Toxaphene, a ChlorinatedHydrocarbon with Insecticidal Properties," February 1947.

Desalbres et al., Chimie and Industrie, Volume 58, Number 5, November1947, pages 443 to 448.

1. AN INSECTICIDAL COMPOSITION COMPRISING THE PRODUCT OF CHLORINATION INAN INERT SOLVENT WITH CHLORINE GAS IN THE PRESENCE OF A REERADICALFORMING CHLORINATION CATALYST AT A TEMPERATURE IN THE RANGE OFABOUT 50* C. TO ABOUT 150* C. TO A CHLORINE CONTENT OF ABOUT 40-70% OFAN OXYTERPENE MATERIAL OF THE GROUP CONSISTING OF ISOBORNYL ACETATE,ISOBORNYL CHLOROACETATE, ISOBORNYL PROPIONATE, BORNYL SALICYLATE,FENCHYL ALCOHOL, ISOBORNEOL AND TERPINYL CHLOROETHYL ETHER AND ANINSECTICIDAL ADJUVANT AS A CARRIER THEREFOR.